Polyolefin-chelate compositions having improved dye receptivity



they give rise to a decomposition of the polyolefins so United States Patent "ice 3,248,378

Patented Apr. 26, 1966 HA n or the aluminum salt of the acetoacetic ester of the fol- Horst Behrenhruch, Kelkheim, Taunus, Wilhelm Happe, lowing Formula 4 Schwalhach, Taunus, Gerhard Freitag, Niederhofheim,

Taunus, and Hans Hoyer, Frankfurt am Main, Ger- CH5 O (|3TO\ J0 O|- OO2HB many, assignors to Farbwerke Hoechst Alitieiigesell-- CH 1' CH schaft vormals Meister Lucius & Bruning, Frankfurt g g am Main, Germany, a corporation of Germany 3 3 No Drawing. Filed Oct. 8, 1962, Ser. No. 229,170 0 0 Claims priority, application (52ermany,.0ct. 10, 1961, L

F 35,1 4 Claims. (Cl. 260-935) (3H3 CI)O2H5 The present invention relates to a process for the manu- F 1 4 facture of improved shaped articles of linear polyolefins. Ormu a Linear polyolefins obtained by the polymerization of olefins, for example, linear polyethylene and polypropylene, are diificult to color. To remove this drawback, the polyolefins are admixed, before being worked up into The aforesaid substances may alsobe used in admixture with One another, the mixtures being added to the polyolefins in the above mentioned amounts.

By the addition of the aforesaid compounds in accord- Z21 5? i g i fi g? fig i s l fi ay ance With the invention, the dye receptivity of the polyolehydrogddes 3 2 m an Zlrc mum or elf OX1 fins is improved to a surprisingly high degree, without the Such additions "have the disadvantage however that ultimate tensile strength, elongation at break and bending strength, being impaired. Nor does the addition of the said compounds interfere with the working up of the difficulties. Moreover the temperature stability of the 25 polyolefins into filaments or filters from the melt. :ianpted articles, especially filaments and fibers, 1S insufii- The above mentioned chromium or aluminum I pounds are advantageously added to the polyolefins in a melllgwalwg fling: gou gldegisatozhfigzglragggziesgigi fajrfii: manner such that the polyolefins and the chromium tlir ample polyethylene or polypropylene, which have Particw aluminum compounds are intimately mixed in a fine y that the forming of such polyolefins is often beset with larly good dye receptivity, can be obtained by adding to ground When i mlxture so obtameii f the polyolefins to be Worked up 07 to 3% by weight, the chromium or aluminum compounds are distributed in advantageously 0.5 to 2% by weight, of chromium steai fig completely ig i g It rate, aluminum stearate or chromium acetyl acetonate of 1S a so P0851 Owever 0 Prepare e mm mm y i the following Formula 1 pregnating the granulated or powdered polyolefin with a solution or dispersion of the chromium or aluminum CH3 (|3=O O=() CH3 compounds, removing the solvent by evaporation and EH' ,1" 3 then thoroughly mixing the polyolefin on which the compounds have been left behind. Alternatively, first 3 0 a mixture of a polyolefin containing a relatively high por- 1 ll tion of the above mentioned compounds is prepared, the

fi 'fi mixture is then melted, the melt is spun into a band C 3 C 3 which is worked up into chips (small pieces) which, in Formula 1 turn, are added to the remaining portion of the polyolefin or aluminum acetyl aceto-nate of the following Formula 2 prior to the working up of the polyolefin so that a mix- CH (IJ=O 0=C|1CH ture having a desired content of chromium or aluminum C H compounds in a given case is obtained. ll The following examples serve to illustrate the inven- CH3C O-A1:?C CH3 tion but they are not intended to limit it thereto, the

| parts being by weight. (|]=CH(|3 Example 1 CH3 CH3 Formula 2 995 parts of powdered polypropylene having a relative or the chromium salt of the acetonacetic ester of the folglsgoslty of L8 (determmeodon a i m f i lowing Formula 3 y ronaphthalene at 135 C.) were intimate y mixe with 5 parts of aluminum stearate in a fluid mixer. The

C2H5O (|3=0 O=C O-C2H5 mixture was spun into yarns at 270 C. with the use of a (311 1" 6Q heated screw extruder. The yarns had a titre of 270 CH (iO CiOC CH deniers and consisted of 24 individual filaments. The filaments were drawn off from the spinning nozzle at a I I! rate of 1000 meters per minute. The filaments were then (13:61??? drawn at a temperature within the range of to C.

CH; 0-0211 65 in a ratio of 1:3.65. The drawn filaments had an ultimate Formula 3 tensile strength of 3.6 grams per denier and an elongaother properties of the polyolefins, for example viscosity,

n tion at break of 25%. They could be well colored with the following dyestuffs:

Example 2 99 parts of granulated polypropylene having a relative viscosity of 2.1 (determined as described in Example 1) were intimately mixed with 1 part of powdered aluminum stearate dispersed in 19 parts of methanol. The methanol was then removed from the mixture by evaporation and the mixture was stirred again. The granules were worked up from the melt in the manner described in Example 1. The filaments so obtained had an ultimate tensile strength of 3.3 to 3.5 grams per denier and an elongation at break of 21 to 25%. The filaments could be well colored with the dyestulfs mentioned in Example 1.

Example 3 995 parts of powdered polypropylene having a relative viscosity of 2.1 (determined as described in Example 1) were intimately mixed with parts of chromium stearate in a fluid mixer. The mixture Was worked up to filaments as described in Example 1. The filaments so obtained had good technological properties and could be well colored with the dyestuffs mentioned in Example 1.

Example 4 99 parts of powdered polypropylene having a relative viscosity of 1.9 (determined as described in Example 1) were intimately mixed with 1 part of chromium stearate in a fluid mixer. The mixture was made into filaments as described in Example 1. The filaments so obtained had good technological properties and could be well colored with the dyestuffs mentioned in Example 1.

Example 5 995 parts of polypropylene having a relative viscosity of 1.8 (determined as described in Example 1) were mixed with 5 parts of aluminum acetyl acetonate as described in Example 1 and worked up into filaments. The filaments so obtained had an ultimate tensile strength of 3.5 to 4.0 grams per denier and an elongation at break of 25 to 35%. They could be well colored deep shades with the dyestuffs mentioned in Example 1.

Example 6 99 parts of granulated polypropylene having a relative viscosity of 2.1 (determined as described in Example 1) were intimately mixed with 1 part of aluminum acetyl acetonate dispersed in 19 parts of methanol. The methanol was subsequently removed from the mixture by evaporation and the mixture was stirred again. The granules were worked up from the melt as described in Example 1. The filaments so obtained had an ultimate 4 tensile strength of 3.5 to 4.0 grams per denier and an elon- 'gation at break of 25 to 35%. They could be well colored with acid dyestuffs.

Example 7 995 parts of powdered polypropylene having a relative viscosity of 2.1 (determined as described in Example 1) were intimately mixed with 5 parts of chromium acetyl acetonate in a fluid mixer. The mixture was made into filaments as described in Example 1. The filaments so obtained had gOOd technological properties. They could be well colored with the dyestuffs mentioned in Example 1. The filaments had an ultimate tensile strength of 3.5 to 4.0 grams per denier and an elongation at break of 25 to 35%.

Example 8 99 parts of powdered polypropylene having a relative viscosity of 1.9 (determined as described in Example 1) were intimately mixed with 1 part of chromium acetyl acetonate in a fluid mixer. The mixture was made into filaments as described in Example 1. The filaments so obtained had an ultimate tensile strength of 3.5 to 4.0 grams per denier and an elongation at break of 25 to 35%. The filaments could be colored deep shades with the dyestuffs mentioned in Example 1.

We claim:

1. In a process for the manufacture of dye receptive shaped articles of a polyolefin selected from the group consisting of polyethylene and polypropylene comprising adding to the polyolefin before it is processed into a shaped article a compound for improving the dye receptivity of said polyolefin, and processing the mixture into shaped articles, the improvement of adding as said compound 0.1 to 3% of a compound selected from the group consisting of chormium acetyl acetonate, aluminum acetyl acetonate, chromium acetoacetic ester and aluminum acetoacetic ester.

2. The process of claim 1 wherein 0.52.0% of said compound is added to the polyolefin.

3. The composition of matter according to claim 4 wherein said composition contains 0.52.0% of said metal compound.

4. A dye receptive composition of matter from which shaped articles are formed consisting essentially of a polyolefin selected from the group consisting of polyethylene and polypropylene containing 0.1 to 3% by weight of a metal compound selected from the group consisting of chromium acetyl acetonate, aluminum acetyl acetonate, chromium acetoacetic ester and aluminum acetoacetic ester.

References Cited by the Examiner UNITED STATES PATENTS 2,984,634 5/1961 Caldwell et al 26023 3,164,438 1/1965 Thomas 855 3,169,043 2/1965 Baumgartner 855 3,169,823 2/1965 Gagliardi 855 DONALD E. CZAJA, Primary Examiner.

LEON I. BERCOVITZ, Examiner. 

4. A DYE RECEPTIVE COMPOSITION OF MATTER FROM WHICH SHAPED ARTICLES ARE FORMED CONSISTING ESSENTIALLY OF A POLYOLEFIN SELECTED FROM THE GROUP CONSISTING OF POLYETHYLENE AND POLYPROPYLENE CONTAINING 0.1 TO 3% BY WEIGHT OF A METAL COMPOUND SELECTED FROM THE GROUP CONSISTING OF CHROMIUM ACETYL ACETONATE, ALUMINUM ACETYL ACETONATE, CHROMIUM ACETOACETIC ESTER AND ALUMINUM ACETOACETIC ESTER. 